CN114959313B - Leaching agent, method and preparation of lead-zinc leaching slag and recovery method of lead-zinc replacement slag - Google Patents
Leaching agent, method and preparation of lead-zinc leaching slag and recovery method of lead-zinc replacement slag Download PDFInfo
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- C22B41/00—Obtaining germanium
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Abstract
The invention provides a leaching agent, a leaching method and a leaching preparation method for lead-zinc leaching residues and a recycling method for lead-zinc replacement residues. The solvent of the germanium gallium leaching agent is water, and the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions. The solubility of sulfate ions is 1-4 mol/L, the solubility of acetate ions is 0.1-0.5 mol/L, and the concentration of ammonium ions is 0.1-0.5 mol/L. Acetate can react with lead-copper compounds in lead-zinc leaching slag to destroy lead-copper compounds, such as green lead ores which are difficult to dissolve by sulfuric acid, so as to release germanium and gallium embedded in ore phases. Ammonium has complexing effect and can react with germanium and gallium to form soluble complex. In this way, the sulfate ions can leach germanium and gallium. The germanium gallium leaching agent has low reagent cost, reduces leaching cost, has high leaching efficiency on germanium and gallium, and improves the resource utilization rate of lead-zinc leaching slag.
Description
Technical Field
The invention relates to the technical field of reinforcement recovery of scattered elements, in particular to a leaching agent and method for lead-zinc leaching slag, preparation and a recovery method for lead-zinc replacement slag.
Background
Germanium is located between tin and silicon in the transition from metal to non-metal and therefore also has good semiconductor properties such as holes, good electron mobility etc. and conductivity properties typically are also between non-metal and metal. Germanium is an important semiconductor metal and has wide application in the fields of optical fiber communication, infrared optics, solar cells, polymer catalysts, medical treatment and the like. Gallium compounds are excellent semiconductor materials and can be used as raw materials for microwave communication, infrared detectors and light emitting diodes. With the rapid development of technology, germanium and gallium are increasingly applied to the high-tech industry, and are very promising industrial metal raw materials.
The lead-zinc replacement slag has a certain content of germanium and gallium, so that the recovery and extraction of the germanium and the gallium from the lead-zinc replacement slag has higher industrial value. Germanium and gallium extraction technology can be divided into two types, namely a fire method and a wet method, but the traditional fire method is high in energy consumption and not friendly to the environment due to low efficiency of the fire method technology process. Therefore, the current industry uses normal pressure acid leaching and oxygen pressure acid leaching to extract germanium and gallium from the replacement slag is the mainstream method. However, the existing states of germanium and gallium in the actual slag are complex, the distribution is scattered, and a lot of germanium and gallium coexist along with other phases, so that the germanium and gallium are difficult to recycle through conventional acid leaching, and a large amount of germanium and gallium resources are not utilized and lost in the leached tailings (namely lead-zinc leached slag).
Related strengthening leaching methods for lead-zinc leaching slag comprise oxygen pressure acid leaching, external field strengthening leaching, leaching aid strengthening and the like. However, the related intensified leaching methods basically have the defects of low leaching efficiency and difficult utilization of tailings resources.
Disclosure of Invention
The invention mainly aims to provide a leaching agent, a leaching method and a leaching preparation method for lead-zinc leaching residues and a recycling method for lead-zinc replacement residues, so as to solve the technical problems of low leaching efficiency and difficult utilization of tailings resources in the related enhanced leaching method.
In order to achieve the above object, a first aspect of the present invention provides a gallium germanium leaching agent, wherein the solvent of the gallium germanium leaching agent is water, and the gallium germanium leaching agent includes sulfate ions, acetate ions and ammonium ions. The solubility of sulfate ions is 1-4 mol/L, the solubility of acetate ions is 0.1-0.5 mol/L, and the solubility of ammonium ions is 0.1-0.5 mol/L.
The second aspect of the invention provides a method for preparing a germanium gallium leachable agent, comprising the following steps:
mixing sulfuric acid, an auxiliary leaching agent and water to obtain the germanium gallium leaching agent, wherein the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions. The solubility of sulfate ions is 1-4 mol/L, the solubility of acetate ions is 0.1-0.5 mol/L, and the solubility of ammonium ions is 0.1-0.5 mol/L. The leaching aid comprises a compound that is dissolved in water to produce and/or reacts with at least one of water, sulfuric acid to produce acetate ions and ammonium ions.
Alternatively, the solubility of sulfate ions is 1-2 mol/L, the solubility of acetate ions is 0.125-0.25 mol/L, and the solubility of ammonium ions is 0.125-0.25 mol/L.
Optionally, the leaching aid is ammonium acetate.
The third aspect of the invention provides a leaching method of lead-zinc leaching slag, comprising the following steps:
and (3) placing the lead-zinc leaching slag into a germanium-gallium leaching agent for leaching to obtain germanium-gallium-enriched leaching liquid. The solvent of the germanium gallium leaching agent is water, and the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions. The solubility of sulfate ions is 1-4 mol/L, the solubility of acetate ions is 0.1-0.5 mol/L, and the solubility of ammonium ions is 0.1-0.5 mol/L.
Optionally, the liquid-solid ratio of the lead-zinc leaching slag to the germanium-gallium leaching agent is 8-12 mL/g, the leaching temperature is 50-100 ℃, and the leaching time is 0.5-5 h; stirring is carried out in the leaching process, and the stirring rotating speed is 200-250 rpm.
Optionally, the liquid-solid ratio of the lead-zinc leaching slag and the germanium-gallium leaching agent is 10mL/g, the leaching temperature is 80-90 ℃, and the leaching time is 2h.
Optionally, the lead-zinc leaching slag is in a powder form, and the grain size of the lead-zinc leaching slag is 60 mu m.
The fourth aspect of the invention provides a method for recycling germanium gallium from lead-zinc replacement slag, which comprises the following steps:
and carrying out at least one leaching cycle on the lead-zinc displacement slag to obtain lead-zinc leaching slag, wherein the leaching cycle comprises the steps of slag sample drying, slag sample leaching and slag and leaching liquid separation which are sequentially carried out, and the leaching slag obtained in the former leaching cycle is used as a slag sample in the latter leaching cycle.
And leaching the lead-zinc leaching slag by adopting the leaching method.
Optionally, the lead zinc displacement slag is subjected to three leaching cycles.
In the leaching step of the first leaching cycle, 80-120 g/L sulfuric acid is used as the leaching agent, and the leaching time is 1-2 h.
In the leaching step of the second leaching cycle, 100-120 g/L sulfuric acid is used as the leaching agent, and the leaching time is 2-4 h.
In the leaching step of the third leaching cycle, 120-140 g/L sulfuric acid is used as the leaching agent, and the leaching time is 2-4 h.
In the germanium gallium leaching agent, the main mineral phases of lead-zinc leaching slag are silicon dioxide, lead sulfate, green lead ore (Linarite) and limonite. Acetate can react with the green lead ore in the lead-zinc leaching slag to destroy the green lead ore which is difficult to dissolve by sulfuric acid, thereby releasing germanium and gallium which are embedded in the ore phase. Ammonium has complexing effect and can react with germanium and gallium to form soluble complex. As one, the sulfate ions leach germanium and gallium. The germanium gallium leaching agent has low reagent cost, reduces leaching cost, has high leaching efficiency on germanium and gallium, and improves the resource utilization rate of lead-zinc leaching slag.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a process for strengthening germanium and gallium leaching from lead-zinc triple leaching residues in the invention;
FIG. 2 is a graph of the leaching rate of multi-stage leached germanium in example 1;
FIG. 3 is a graph of multi-stage gallium leach leaching in example 1;
FIG. 4 is a graph showing the leaching efficiency of germanium and gallium from the triple leaching residue at different ammonium acetate dosages in example 2;
FIG. 5 is a graph showing the leaching efficiency of germanium and gallium from the triple leached residues at different leaching times in example 2;
FIG. 6 is a graph showing the leaching efficiency of germanium and gallium from the triple leached residues at different leaching temperatures in example 2;
fig. 7 is a spectrum of XRD phase analysis before and after leaching in example 2.
The achievement of the object, functional features and advantages of the present invention will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
It should be noted that all directional indicators (such as upper and lower … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.
It should be appreciated by those skilled in the art that as an illustration of the present application, dosage in the figures may be expressed as an administered dose, intensity as intensity or saturation, theta degree as diffraction angle, leaching efficiency as leaching efficiency, and wavenumber without affecting a practical understanding of the technical solution of the present application.
The embodiment of the application provides a germanium gallium leaching agent, wherein a solvent of the germanium gallium leaching agent is water, and the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions; the solubility of sulfate ions is 1-4 mol/L, the solubility of acetate ions is 0.1-0.5 mol/L, and the solubility of ammonium ions is 0.1-0.5 mol/L.
The lead-zinc leaching slag is the leaching slag of lead-zinc replacement slag. The lead-zinc displacement slag is leached in multiple stages (e.g., 1-3 stages). The specific operation method of the multistage leaching is that the obtained lead-zinc displacement slag is leached in a multistage way by normal pressure acid leaching, and the slag sample drying-normal pressure leaching-solid-liquid separation in the multistage leaching process is a leaching cycle. The solids (i.e., leached residues) in the solid-liquid separation of the previous leaching cycle are the slag sample (i.e., the material to be leached) of the subsequent leaching cycle.
Leaching the lead-zinc displacement slag in the first section to obtain leaching slag called lead-zinc primary leaching slag; the leaching residue obtained by leaching the lead-zinc displacement slag in the second stage, namely the leaching residue obtained by leaching the lead-zinc primary leaching residue in the second stage, can be called lead-zinc secondary leaching residue. Similarly, lead-zinc displacement slag is generally leached in three stages, namely lead-zinc displacement slag is obtained to obtain lead-zinc triple leaching slag. Of course, if necessary, the lead-zinc displacement slag can also be leached in more stages, so as to obtain corresponding lead-zinc leaching slag.
In this embodiment, the germanium gallium leaching agent is used for leaching lead-zinc leaching slag, and the lead-zinc leaching slag is not particularly limited. The lead-zinc leaching slag can be one or more of lead-zinc leaching slag, lead-zinc leaching slag and the like.
Since lead-zinc displacement slag is typically subjected to three-stage leaching (see below for specific analysis), the lead-zinc triple leaching slag is illustrated herein as being leached by a germanium gallium leachable agent.
The inventors have found through a great deal of research that the slag occurrence state of the lead-zinc three-leaching slag is complex, and the main mineral phases of the slag are silicon dioxide, lead sulfate, green lead ore (Linarite) and limonite. Residual portions of germanium and gallium may be embedded in iron-based compounds and lead-copper compounds as isomorphic impurities, and are difficult to further leach with sulfuric acid.
Based on this, a germanium gallium leachable agent is provided. The germanium gallium leachable agent comprises sulfate ions, acetate ions and ammonium ions. Acetate can react with lead-copper compounds in lead-zinc leaching slag to destroy lead-copper compounds, such as green lead ores which are difficult to dissolve by sulfuric acid, so as to release germanium and gallium embedded in ore phases. Ammonium has complexing effect and can react with germanium and gallium to form soluble complex. As one, the sulfate ions leach germanium and gallium.
Under the conditions that the solubility of acetate ions is 0.1-0.5 mol/L and the solubility of ammonium ions is 0.1-0.5 mol/L, the leaching rate of gallium and germanium is higher. Under the condition that the solubility of acetate ions and ammonium ions is too small, the leaching rates of gallium and germanium are relatively low, and under the condition that the solubility of acetate ions and ammonium ions is too large, the leaching rates of gallium and germanium are also reduced, the reagent use amount is increased, and the cost is increased. The solubility of the acetate ion and the solubility of the ammonium ion may be the same or different.
In the germanium gallium leaching agent, the main mineral phases of lead-zinc leaching slag are silicon dioxide, lead sulfate, green lead ore (Linarate) and limonite. Acetate can react with lead-copper compounds in lead-zinc leaching slag to destroy lead-copper compounds, such as green lead ores which are difficult to dissolve by sulfuric acid, so as to release germanium and gallium embedded in ore phases. Ammonium has complexing effect and can react with germanium and gallium to form soluble complex. As one, the sulfate ions leach germanium and gallium. The germanium gallium leaching agent has low reagent cost, reduces leaching cost, has high leaching efficiency on germanium and gallium, and improves the resource utilization rate of lead-zinc leaching slag.
The embodiment of the application also provides a preparation method of the germanium gallium leaching agent, which comprises the following steps:
mixing sulfuric acid, an auxiliary leaching agent and water to obtain the germanium gallium leaching agent, wherein the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions. The solubility of sulfate ions is 1-4 mol/L. The solubility of the acetate ion is 0.1 to 0.5mol/L. The solubility of ammonium ions is 0.1 to 0.5mol/L. The leaching aid comprises a compound that is dissolved in water to produce and/or reacts with at least one of water, sulfuric acid to produce acetate ions and ammonium ions.
In the above preparation method, the leaching aid may be a single compound or a mixture formed by mixing a plurality of compounds. The leaching aid may be dissolved in water to produce acetate and ammonium ions (e.g., ammonium acetate, infra), or may be reacted with sulfuric acid, water to produce acetate and ammonium ions; of course, the acetate ion and the ammonium ion may be obtained by both of the above methods. And are not limited herein.
Illustratively, the leaching aid may be a mixture of acetic acid and ammonium chloride, a mixture of acetic acid and ammonium sulfate, a mixture of acetic acid and ammonium nitrate, or a mixture of sodium acetate and ammonium nitrate.
Optionally, the leaching aid is ammonium acetate.
The chemical structural formula of the ammonium acetate is as follows:
thus, ammonium acetate is dissolved in water to produce acetate ions and ammonium ions. In the mode, other elements are not introduced, and influence on leaching results by other elements is reduced. In addition, the preparation method is simple, and the concentrations of acetate ions and ammonium ions can be controlled more accurately.
Optionally, the solubility of sulfate ions is 1-2 mol/L. The solubility of the acetate ions is 0.125-0.25 mol/L. The solubility of the ammonium ions is 0.125-0.25 mol/L. For example, it may be prepared as ammonium acetate: concentrated sulfuric acid: aqueous solution = 1-2 g: 8-10 g: the mixture ratio of 90-110 mL is used for preparation.
The embodiment of the application also provides a leaching method of the lead-zinc leaching slag, which comprises the following steps:
and (3) placing the lead-zinc leaching slag into a germanium-gallium leaching agent for leaching to obtain germanium-gallium-enriched leaching liquid. Wherein the solvent of the germanium gallium leachable agent is water. The germanium gallium leachable agent comprises sulfate ions, acetate ions and ammonium ions. The solubility of sulfate ions is 1-4 mol/L. The solubility of the acetate ion is 0.1 to 0.5mol/L. The solubility of ammonium ions is 0.1 to 0.5mol/L.
The leaching method of the lead-zinc leaching slag has the advantages of lower reagent cost, reduced leaching cost, high leaching efficiency of germanium and gallium and improved resource utilization rate of the lead-zinc leaching slag.
Optionally, the liquid-solid ratio of the lead-zinc leaching slag to the germanium-gallium leaching agent is 8-12 mL/g, the leaching temperature is 50-100 ℃, and the leaching time is 0.5-5 h; stirring is carried out in the leaching process, and the stirring rotating speed is 200-250 rpm.
Under the condition, the leaching rate of germanium and gallium is higher, and the leaching cost is lower.
Optionally, the liquid-solid ratio of the lead-zinc leaching slag and the germanium-gallium leaching agent is 10mL/g, the leaching temperature is 80-90 ℃, and the leaching time is 2h.
Under the condition, the leaching rate of germanium and gallium is further improved, and the leaching cost is further reduced.
In order to further increase the leaching rate of the lead-zinc leaching slag, in some embodiments, the lead-zinc leaching slag is in the form of a powder, and the grain size of the lead-zinc leaching slag is 60-100 μm. The lead-zinc leaching residue can be firstly dried, crushed and ground to form powder.
Illustratively, the drying temperature during the drying operation is 70-100 ℃; the drying operation time is 8-16 h. Under the condition, the lead-zinc leaching slag is thoroughly dried, so that the subsequent crushing and grinding steps are facilitated.
After the germanium-gallium-enriched leaching solution is obtained, a solid-liquid separation step can be further included, the solid-liquid separation operation adopts a filter screen for separation, and the pore diameter of the filter screen can be 0.45 mu m.
The embodiment of the application also provides a method for recycling germanium gallium from lead-zinc replacement slag, which comprises the following steps:
and carrying out at least one leaching cycle on the lead-zinc displacement slag to obtain lead-zinc leaching slag, wherein the leaching cycle comprises the steps of slag sample drying, slag sample leaching and slag and leaching liquid separation which are sequentially carried out, and the leaching slag obtained in the former leaching cycle is used as a slag sample in the latter leaching cycle.
And leaching the lead-zinc leaching slag by adopting the leaching method.
The lead-zinc displacement slag can be leached by adopting an atmospheric pressure sulfuric acid multistage leaching method, and can be leached by adopting other leaching agents, and the specific leaching process is described above and is not described in detail.
Optionally, the lead zinc displacement slag is subjected to three leaching cycles.
In the leaching step of the first leaching cycle, 80-120 g/L sulfuric acid is used as the leaching agent, and the leaching time is 1-2 h.
In the leaching step of the second leaching cycle, 100-120 g/L sulfuric acid is used as the leaching agent, and the leaching time is 2-4 h.
In the leaching step of the third leaching cycle, 120-140 g/L sulfuric acid is used as the leaching agent, and the leaching time is 2-4 h.
Example 1
And (3) multi-stage leaching of lead-zinc replacement slag and representation of slag sample element content:
multi-stage leaching of lead-zinc displacement slag
1. One-stage leaching of lead-zinc displacement slag
And taking lead-zinc replacement slag retrieved from a certain smelting plant as raw slag to carry out primary leaching. Setting the concentration of sulfuric acid as 100g/L, the volume of the leaching agent as 100ml, leaching the zinc smelting displacement slag at 80 ℃ under the conditions of 10ml/g of liquid-solid ratio, 250rpm of oscillation speed and 1h of leaching time, and carrying out solid-liquid separation after leaching to obtain lead-zinc primary leaching slag.
2. Lead-zinc primary leaching slag two-stage leaching
Taking the obtained lead-zinc primary leaching slag as raw slag to carry out secondary leaching. Setting the concentration of sulfuric acid to be 120g/L, setting the volume of a leaching agent to be 100ml, leaching the zinc smelting displacement slag under the conditions of 80 ℃ of temperature, 250rpm of oscillation speed and 2 hours of leaching time, and carrying out solid-liquid separation after leaching to obtain lead-zinc secondary leaching slag.
3. Three-stage leaching of lead-zinc secondary leaching slag
And taking the obtained lead-zinc secondary leaching slag as raw slag to carry out three-stage leaching. Setting the sulfuric acid concentration to 140g/L, leaching the zinc smelting displacement slag under the conditions that the temperature is 80 ℃, the oscillating speed is 250rpm and the leaching time is 3 hours, and obtaining three sections of leaching residues through solid-liquid separation after the leaching is completed.
(II) determination of leaching rate of germanium and gallium by multistage leaching
1. Multi-stage germanium leaching rate determination
And measuring the leaching concentration of germanium in the zinc leaching solution by adopting an inductively coupled plasma spectrum generator (ICP-OES), so as to calculate and obtain the germanium leaching rate of different leaching sections. As shown in fig. 2, the leaching rates of germanium from the first leaching stage to the third leaching stage were 60.9%, 79.1% and 85.1%, respectively. The result shows that the increase of the leaching stage number has a certain promotion effect on germanium, but the degree of improvement of the leaching rate gradually decreases with the increase of the leaching stage number.
2. Multi-stage germanium leaching rate determination
The leaching rates of gallium leached from the first stage to the third stage were measured and, as shown in fig. 3, were 81.1%, 94.5% and 95.9%, respectively. The result shows that the second-stage leaching has obvious promotion effect on gallium, but the degree of improvement of the leaching rate is obviously reduced along with the increase of the number of the leaching stages to the third stage, and the subsequent continuous normal-pressure sulfuric acid leaching has limited improvement on the leaching efficiency.
Example 2
Leaching of germanium and gallium in ammonium acetate reinforced lead-zinc three-leaching slag
Under the optimized experimental conditions, a sulfuric acid solution with the concentration of 100g/L is prepared, the leaching temperature is regulated to 80 ℃, the liquid-solid ratio is regulated to 10mL/g, the oscillating speed is regulated to 200rpm, the leaching time is regulated to 2 hours, 0.2mM ammonium acetate is added into the three leaching residues, and no leaching aid is added to be used as a control group. The analysis and determination are carried out by ICP-OES, 3 different adsorption band values are taken, and the minimum value of the RSDs is selected as the data reference.
The leaching performance of ammonium acetate reinforced germanium and gallium is explored by independently adjusting the addition amount, the leaching temperature and the leaching time parameters of the leaching aid, and the specific steps are as follows:
influence of various leaching parameters on leaching performance of ammonium acetate enhanced germanium and gallium
1. Infusion aid dosage
As shown in fig. 4, under the above-described optimized experimental conditions, the leaching rates of gallium and germanium increased and then decreased as the concentration of ammonium acetate added increased. In the interval of 0mol/L to 0.2mol/L, the leaching rate of gallium and germanium is obviously improved, the leaching rate of gallium is improved from 96.2 percent to 97.7 percent, the leaching rate of germanium is improved from 95.3 percent to 98.0 percent, the ammonium acetate has obvious effect on improving the leaching rate of gallium and germanium, when the concentration is more than 0.2mol/L, the leaching rates of gallium and germanium are in a descending trend, the leaching of gallium and germanium is not facilitated, the industrial cost and the leaching efficiency are comprehensively considered, and the optimal concentration of ammonium acetate is determined to be 0.2mol/L.
2. Leaching temperature
As shown in fig. 5, under the above-mentioned optimized experimental conditions, the leaching rates of gallium and germanium fluctuate up and down with the rise of the temperature at 50 to 100 ℃. The leaching rate of gallium is continuously increased at 60-80 ℃, and the leaching rate of gallium reaches the maximum value of 97.7% at 80 ℃. The leaching rate of germanium is continuously increased at 60-90 ℃, and the leaching rate of germanium reaches the maximum value of 98.6% at 90 ℃. However, as the temperature continues to rise, the leaching rates of gallium and germanium decrease. The leaching cost and the process effect are comprehensively considered, and the optimal leaching temperature range is determined to be 80-90 ℃.
3. Leaching time
As shown in fig. 6, under the above-described optimized experimental conditions, the leaching rates of gallium and germanium increased greatly and then increased slightly with increasing leaching time at a leaching time of 0.5h to 5 h. When the leaching time is 0.5-2 h, the leaching rate of gallium and germanium is obviously increased, the leaching rate of gallium is increased from 95.4% to 96.7%, and the leaching rate of germanium is increased from 93.4% to 96.6%. When the leaching time is 2-5 h, the leaching rate of gallium and germanium is raised to be smaller, the leaching rate of gallium is raised to 97.6% from 96.7%, and the leaching rate of germanium is raised to 98.4% from 96.6%. And comprehensively considering the leaching efficiency and the process cost, and determining the optimal leaching time to be 2h.
Mechanical study of (II) ammonium acetate leaching aid
As shown in fig. 7, the main ore phases of the leaching residue are silicon dioxide, lead sulfate, green lead ore (Linarate) and limonite (Hohmannite), and the diffraction peak of the green lead ore is significantly reduced or disappeared after ammonium acetate is added. This is attributable to the fact that ammonium acetate can react with lead-copper compounds in the triple leach residue, destroying lead-copper compounds that are the green lead ore that are difficult to dissolve in sulfuric acid, and releasing germanium and gallium that are embedded in the ore phase. In addition, acetic acid is an organic acid, and ammonium has the capacity of forming coordination complexes, and can react with germanium and gallium to form soluble complexes. From these results, it can also be inferred that part of the germanium and gallium remaining in the triple leaching residue may be embedded in the iron-based compound and lead-copper compound as isomorphic impurities, and it is difficult to further leach with sulfuric acid.
In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and therefore, the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the description of the present invention and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.
Claims (10)
1. The germanium gallium leaching agent is characterized in that the germanium gallium leaching agent is used for leaching lead-zinc leaching slag, the main mineral phases of the lead-zinc leaching slag are silicon dioxide, lead sulfate, green lead ore and limonite, and germanium and gallium are embedded in the mineral phases of the green lead ore;
the solvent of the germanium gallium leaching agent is water, and the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions; the solubility of sulfate ions is 1-4 mol/L, the solubility of acetate ions is 0.1-0.5 mol/L, and the solubility of ammonium ions is 0.1-0.5 mol/L.
2. The preparation method of the germanium gallium leaching agent is characterized by comprising the following steps of:
mixing sulfuric acid, an auxiliary leaching agent and water to obtain the germanium gallium leaching agent, wherein the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions; the solubility of sulfate ions is 1-4 mol/L, the solubility of acetate ions is 0.1-0.5 mol/L, and the solubility of ammonium ions is 0.1-0.5 mol/L; the leaching aid comprises a compound that is dissolved in the water to produce and/or reacts with at least one of the water and the sulfuric acid to produce acetate ions and ammonium ions.
3. The method for preparing a gallium germanium leachable agent according to claim 2, wherein the solubility of sulfate ions is 1 to 2mol/L, the solubility of acetate ions is 0.125 to 0.25mol/L, and the solubility of ammonium ions is 0.125 to 0.25mol/L.
4. A method of preparing a gallium germanium leachable agent as defined in claim 2 or claim 3, wherein the leaching aid is ammonium acetate.
5. The leaching method of the lead zinc leaching slag is characterized by comprising the following steps of:
placing the lead-zinc leaching slag into a germanium-gallium leaching agent for leaching to obtain germanium-gallium-rich leaching liquid; the germanium gallium leaching agent is prepared from a solvent, wherein the solvent of the germanium gallium leaching agent is water, and the germanium gallium leaching agent comprises sulfate ions, acetate ions and ammonium ions; the solubility of sulfate ions is 1-2 mol/L, the solubility of acetate ions is 0.125-0.25 mol/L, and the solubility of ammonium ions is 0.125-0.25 mol/L; the main mineral phases of the lead-zinc leaching slag are silicon dioxide, lead sulfate, green lead ore and limonite, and germanium and gallium are embedded in the mineral phases of the green lead ore.
6. The leaching method of the lead-zinc leaching slag according to claim 5, wherein the liquid-solid ratio of the lead-zinc leaching slag to the germanium-gallium leaching agent is 8-12 mL/g, the leaching temperature is 50-100 ℃, and the leaching time is 0.5-5 h; stirring is carried out in the leaching process, and the stirring rotation speed is 200-250 rpm.
7. The leaching method of the lead-zinc leaching slag according to claim 6, wherein the liquid-solid ratio of the lead-zinc leaching slag to the germanium-gallium leaching agent is 10mL/g, the leaching temperature is 80-90 ℃, and the leaching time is 2h.
8. The leaching method of lead-zinc leaching residue according to any one of claims 5 to 7, wherein the lead-zinc leaching residue is in a powder form, and the grain size of the lead-zinc leaching residue is 60 to 100 μm.
9. The method for recycling germanium gallium from lead-zinc replacement slag is characterized by comprising the following steps of:
carrying out at least one leaching cycle on lead-zinc displacement slag to obtain lead-zinc leaching slag, wherein the leaching cycle comprises the steps of slag sample drying, slag sample leaching and slag and leaching liquid separation which are sequentially carried out, and the leaching slag obtained in the former leaching cycle is used as a slag sample in the latter leaching cycle;
leaching the lead-zinc leaching slag by adopting the leaching method of any one of claims 5-8.
10. The method for recycling gallium germanium from lead-zinc displacement slag according to claim 9, wherein the lead-zinc displacement slag undergoes three leaching cycles;
in the leaching step of the first leaching cycle, the leaching agent is 80-120 g/L sulfuric acid, and the leaching time is 1-2 h;
in the leaching step of the second leaching cycle, the leaching agent is 100-120 g/L sulfuric acid, and the leaching time is 2-4 hours;
in the leaching step of the third leaching cycle, the leaching agent is 120-140 g/L sulfuric acid, and the leaching time is 2-4 h.
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| CN102515258A (en) * | 2011-12-12 | 2012-06-27 | 浙江大学 | Method for extracting gallium oxide from bauxite |
| CN103952575B (en) * | 2014-05-13 | 2016-05-11 | 中南大学 | A kind of method that reclaims germanium from germanium-containing material |
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| CN110394238B (en) * | 2019-07-08 | 2020-09-04 | 中国矿业大学(北京) | Homogeneous activation flotation method for copper-lead-zinc multi-metal sulfide ore |
| CN114318017A (en) * | 2021-12-28 | 2022-04-12 | 广东省科学院资源利用与稀土开发研究所 | Method for deep leaching of zinc, copper, gallium and germanium from zinc replacement slag |
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